Treatment of hydrocarbons to remove sulphur compounds



P. c. KEITH, JR

Original Filed Oct. 30, 1935 Oct. 25, 1938.

TREATMENT oF HYDROCARBN'S T o-REMOVE SULPHUR COMPOUNDS Patented ocezaiess y UNITED STATE TREATMENT OF HYDBOCARBONS TO RE- MOVE SULPHUR COMPOUNDS Percival C. Keith, Ir., Peapack, N. J., assgnox; to

Process Management Company,

Inc., New York,

N. Y., a corporationof Delaware Original application October 30, 1935, Serial No.

47,414. Divided and 1938, Serial No. 203,541

3 claims.

` This application is a division of my copending xpilication Serial No. 47,414, filed October 30,

My invention relates to the manufacture of normally liquid gasoline-like hydrocarbons, that is to say, hydrocarbons having boiling points lying within a gasoline or motor-fuel boiling point range, from normally gaseous hydrocarbons of lower molecular weight, and more particularly to a process for. eiecting the conversion or polymerization of hydrocarbon gases produced -inrthe pyrolysis of hydrocarbon oils, and containing both -saturated vand unsaturated hydrocarbon constituents, to-low-boiling, normally liquid gasoline-like products suitable for use as a motor fuel. The products of the pyrolysis of hydrocarbon oils include below the gasoline boiling-point range varying' quantities of hydrogen, methane, ethane, ethylene, propane, propylene, butane and butylenes, and as separated in oil-cracking operations the uncondensable gases may also contain limited quantities of heavier hydrocarbons such as pentane, hexane and other hydrocarbons having ve and six carbon atoms per molecule. It has been known in the art for some time that such gases can be polymerized to higher-boiling normally liquid non-aromatic products under high pressure and at about '750 to 1250 F. I

My invention has for an object thevprovlsion of a process of the character and for the purpose indicated, whereinA hydrocarbon gases such as those produced inthe pyrolytic decomposition of hydrocarbon oils,k after separation Aof hydrogen and methane are converted to normally liquid gasoline-like hydrocarbons of high anti-knock value when used as motor fuel, together with such additional operative improvements and advantages as may hereinafter be foundto obtain.

My invention contemplates av continuous and cyclic process for obtaining low-boiling hydrocarbon liquids of a gasoline-like nature from normally gaseousl hydrocarbons such as those produced in the pyrolysis-or cracking of hydro- `carbon oils, in which gases substantially free from hydrogen and methane are subjectedV to high pressures of from square inch or higher and from about '750 to'1250 but preferably from about 1000 F. to about 1100" F. for a period of timesuiicient to effect thedesired polymerization reactions.l The products of polymerization Vmperatures ranging are cooled to effect the separation, of normally liquid products of gasoline-like nature as well as temperatures ranging from 500 to 3000 pounds perthis application April 22j,

any higher-boiling products which may be formed, and the uncondensed gases and vapors are fractionated to remove hydrogen. .methane and excessive quantities of ethane and then ref cycled. I have found that it is of great importance to fractionate the gases prior to such conversion to separate hydrogen and methane. as completely as possible, and also where necessary to separate ethane to some extent, fully hereinbelow. Suchiractionation may be accomplished upon the composite stock consisting of the ireshieed and the recycled stock, or the fresh feed-and the recycled stock'may be separately fractionated.

Where my process is operated in conjunction with an oil-cracking unit, as willbe made more clear hereinbelow, the fractionation of the gaseous products Vof oil cracking may Vobviously be conducted in different manners prior to their use 20 for polymerization in accordance with our process. Thus, in oil-cracking plants operated at low pressures and producing relatively we gases, such gases may be fractionated after removal of the cracked gasoline herein above, Whereas in oil-cracking plants operating under high pressure, most or all of the constituents desired for Polymerization may be actually removed fromV the condenser in liquid form with the gasoline, to be recovered in the 30 course of stabilization. In some instances, the overhead products from the cracked-gasoline stabilizer may even be suiiiciently free from hydrogen and methane to require no further fractionation prior to conversion.` 4In other in- 35 stances, however, gases from the gas separator ci an oil-cracking unit maybe combined with overhead or reux from the gasoline stabilizer, the combined products then being fractionated vfor the removal of hydrogen 'and methane (as 40 well as all or a portion of the ethane Where desired) prior to conversion. The particular fractionating method employed will depend upon the composition of the normally gaseous products of cracking as well as the pressures and temperatures under which the 'condensation and separation of the cracked gasoline is effected. It will also depend to some extent on whether or not the recycled stock from the gas-conversion unit is separately fractionated Oris recycled to` the 50 oil-cracking operation for fractionation along with the products of cracking.

In orderthat my invention may be fully set iortn and understood, I now describe, withreference to the drawing accompanying and forming if.

as will be explained more 10y inthe manner indicated 25l operation. While a part of this specification, a preferred form and manner in which my invention may be practiced and embodied. Inthe drawing.

'Ihe single ligure is a more or less diagrammatic elevational view of apparatus for eiecting the polymerization of hydrocarbon gases in accordance with my invention, including also apparatus for cracking hydrocarbon oils to produce motor fuel and gases for polymerization, and illustrating an advantageous manner in which an oil-cracking unit may be combined with a gaspolymerizing unit operated in accordance with my invention.

In the instance illustrated in the drawing, I have show n an oil-cracldng unit which is operated for the purpose of reforming naphtha, i. e., of converting naphtha of relatively low -antiknock value into motor fuel of higher anti-knock value. As is well known, such a reforming operation ordinarily results in the formation of considerable quantities of xed gases and constituents lower boiling than are desired to be included in the final lmotor-fuel product. My process makes it possible to effect the conversion of'such gaseous constituents exclusive of hydrogen and methaneto hydrocarbon liquids useful as motor fuel and possessing extremely high anti-knock value, which may be blended, if desired, with the reformed gasoline ,produced in the cracking the gas-polymerizing process of my invention is extremely well suited to combination with a reforming unit of this character, it will be understood by those skilled in the art that my process may be employed in conjunction with other types of oil-cracking operations, for example those operated for the purpose of obtaining gasoline and gases from relatively heavy oils such as gas oil, reduced crude and the like.

Referring now speciiically to the drawing, an oil to be cracked, such for example as a naphtha of relatively low anti-knock value and, it maybe, a naphtha having a slightly higher end boilingpoint than that of the desired nal motor-fuel product, or a relatively heavy oil, such as gas oil, is introduced by means of a pump I and a line 2 wherein is located a heat-exchange coil 3 into a heating'coil 4 located within a suitable heat-'- ing furnace 5. 4, itis subjected to a cracking temperature of, for example, from 850 to 1050 F. and preferably in the instance illustrated to a temperature of about 975 F., under a pressure preferably in excess of 100 pounds per square inch, for example about 800 pounds per square inch or higher, for a suicient values, without materially changing the boiling point range. but on account of the rather vrefractory nature of naphtha, fairly high cracking temperatures are necessary and the production of a considerable amount of gas is practically inevitable.

The heated products from'the pipe coil 4 then pass through a transfer line 8 wherein is located apressure-reducing valve 'I into an evaporator 8 maintained' at a lower pressure than that obtaining in the coil 4.\ By way of example, in the present instance, in which 'a pressure of 800 pounds per square inch is maintained in the coill 4, the evaporator 8 may be maintained at a pres- As the oil passes through .the coil alessia trated. with suitable bailles 9 and with cooling means such as a line I0 wherein is located a pumpI II for introducing a suitable hydrocarbon oil. As the productsv from the transfer line 6 enter the evaporator 8, volatile portions thereof are liberated, and residual portions are withdrawn from the bottom of the evaporator 8 through a valved line I3. YWhere desired, residual oil or tar withdrawnthrough the line I3 may be flashed at a lower pressure in a suitable tar asher (not shown) and distillate thus produced may be returned to the cracking system as, for example, by way of the line I0.

Vapors pass from the evaporator 9 to a fractionating column I5, the interior of which is provided with suitable plates or trays I6 and wherein may be located the heat-exchange coil 3. Passing upward through the fractionating column I5, the vapors are subjected to partial condensation and fractionation for the purpose of condensing sired final gasoline product. A portion of the condensate thus obtained is removed from the trap-out tray I4 through a line I8, wherein may be located a pump I9, and delivered through a branch line 20 having a valve 2| to the transfer line vIi where it is employed for the purpose of quenching the hot products from the coil 4 to a temperature below an active cracking temperature, for example from about 750 to 850 F. Condensate withdrawn through lthe line I8 in excess of that required for quenching the products from the coil 4 is delivered through a line 22 having a valve 23 to the line 2 as recycle stock for the coil 4.

The fractionated overhead vapors from the fractionating column I5 pass through a vapor line 25 to a condenser 26 operated approximately at atmospheric temperature or at any rate employing as a cooling medium water aty atmospheric temperature or a little below, and the partially condensed products then pass through a line 2'I to a gas separator 28 preferably maintained under a pressure slightly below that obtaining in the fractionating column I5, for example about 290 pounds per square inch.

In the separator 28, gasoline condensate separates from uncondensed gases. If the pressure in the separator is high enough, the separated gases may consist substantially entirely of hydrogen and methane at lower pressures, higherboiling constituents may separate in gaseous form. The condensate passes through a line 28 wherein may be located a pump 30 to a gasoline stabilizer or rectifying column 35 provided with suitable'plates or fractionating trays 38, a cooling coil 31 and a heating coil 38. 'I'he stabilizer 35 is operated for the purpose of removing con-v stituents from the condensate which are too light to be included in the final gasoline product, and is preferably held under a superatmospheric pressure at least not materially below that obtaining in the separator 28, for example about 280 pounds per square inch or higher. Stabilized gasoline is withdrawn from the bottom of the stabilizer 25 through a valved line 38, while overhead vapors pass through a vapor line 40to a condenser 4I and thence through -a line 42 into an accumulator 43. Uncondensed gases from the separator 28 are removed therefrom through a line 45 and may pass through a branch line 48 having a valve 41 into the accumulator 43, or may be withdrawn from the system through a branch line 48 having -a valve 48.-

andere 28 are withdrawn from the system or passed to the accumulator of these gases.

erated at high pressure, per square inch, and the 43 will depend upon Where the separator 28 is opfor example 500 pounds the nature separated gases consist -substantially entirely of hydrogen and methane, or of hydrogen, methane and ethane without sub stantial quantities of pro or butylene, they may '10 tem. In such event; the

pane, propylene, butane be removed from the sysoverhead products from the stabilizer ,35, or reux therefrom, may be sufciently free from hydrogen,

methane and ethane to remove the necessity for further fractionation before being subjected to conversion. If, how- 15 ever, the gasesremoved from the separator 28 contain substantial amounts of constituents such as propane, propylene, butane and butylen'e,

they

may be fractionated separately to recover these overhead or reiiux be deprior to be delivered by means yof a valved line 45a to the stabilizer 35.

In the latter instance, from the accumulator 43 through a line 80 and;

gases are withdrawn compressed by means of a pump or compressor 6| to a relatively high pressure of for examplefrom I 300 to 500 pounds per square inch. The -h`eat of compression may be removed'by means of a cooler 30 62 located in ractionator cumulator 43 is delivered gas stabilizer 63 through 35 cated a pump 65,

The compressed gas stabilizer,

or rectifier 63. Liquid from the acto a lower point in the a line 4 wherein is loby means of which such condensate is also placed under a pressure of from 300 to 500 pounds per square inch, or whatever pressure is maintained in the stabilizer t3. A

cooler desired.

tmay be provided in the line 84 if so The gas stabilizer t3 is internally provided with suitable plates or lll located in the toms from the tower liqueed butane, such as pentane, from through a lower trays 10 and with a heating coil portion thereof. Botcomprsing principally as well as heavier hydrocarbons, ii present, arewithdrawn thereline 12 wherein is located a pump lit, and after being passed through a cooler 'i4 are returned to the upper portion of the tower t3 as a reuxing and absorbing medium.

in su`ch manner as to efconstituents thus returned to above atmospheric and preferfrom C. or even lower y gaseous constituents, comprisand methane, are withthe top of the gas stabilizer 83 through a valved linev l5. stabilizer 63 is so conducted that drawn comprise substantially all of the hydrogen The ogperation of the ases thus withand methane Abut are substantially free from higher constitutents, and at any rate preferably do not contain more than 10% of the convertible unsaturated constituents.

65 Where desired, the

be scrubbed-with a s gases ,removed at I may table solvent such as gas oil torecover butane and the like therefrom, the

latter being recovered from the gas fractionator. f

withdrawn as the enriched solvent at an Vintermethrough a line 'll' Y and passes to a stripper 18 having plates or trays v 'i9 and heating means such as the coil 3|! located 'is therein, and wherein any hydrogen, methane and .permitted to pass in l The scrubber |04 may excess ethane contained in the side stream thus withdrawn is driven oi and returned to the gasstabilizer 63 through a line 8|. The` stripped compressed liqud, consisting principally or entirely ofpropane, propylene, butane'and butylene, but sometimes containing some ethane and ethylene as well as some pentane and heavier hydrocarbons, then passes through a line 82 to a vtank While I have illustrated and desc bed a preierred type oi gas-fractionating system', it willbe understood that my invention pects is not limited to the use of the particular type illustrated, as the fractionation of the gases prior to conversion thereof may he accomplished m other suitable manners, if desired. The type of operation illustrated is,'however, well` adapted for use in the process of my invention.

Hydrocarbons collecting in the pass by way of aline 34, wherein may be a pump 85 and valves lllB and 'it As the hydrocarbons-'pass upward through the scrubber |84 they are subjected to countercurrent contact with a iiow of a suitable hydrogensulphide absorbent, such for example as an aqueous solution of sodium hydroxide, sodium carbonate, or any other suitableagent, introduced into the upper portion of the scrubber |84 through a line |85 wherein may be located a pump |06 be provided, as shown, with a plurality .o baiiles ll' or other suitable gasand-liquid-contact devices for contact between the hydrocarbons and the liquid washing medium. Spent washing medium is removed froni the bottom o the scrubber |84 through the valved line |91, while the hydrocarbons thus freed wholly or .to the desired extent from hydrogen sulphide pass through a line ri i8 to a pump lli for compression.

By regulating the pressure on undergoing treatment, as for example by means of the valve 81| and-the compressor 85, removal of hydrogen sulphide may be effected while the hydrocarbons remain in the liquid phase.

It will be obvious to those skilled in the art that various types oi treating solutions may be employed in the scrubber |84. Preferably these will be aqueous in character, especially where the hydrocarbons 'treated are in the liquid phase, inasmuch as aqueous fluids are immscible therewith and may readily be separated therefrom. Instead of employing a solution of caustic soda,

located I may employ various solutions, preferably also tank 83 may promoting eicient the' hydrocarbons in its broader as- 81 to a scrubber tage over'caustic soda solutions in that they may readily be regenerated and re-employed for further hydrogen-sulphide removal.

point can therefore be removed from the system, or where the for use where necessary or desirable.

'I'he hydrocarbons passing through the line ||0 are compressed by means of the pump to a pressure of from 500 to 3000 pounds per time, for example 90 seconds (total time of contact in heating coil and soaker) to effect the desired degree of conversion.

In general, higher,l pressures and high olen' factors of operation.

Ordinarily, I have round that, in operating in' manner set forth herein, the reactions taking e in the soaking coll |2| are not highly exothermic in character, but may be slightlyso, and the heat exchanger or soa-ker |2| i`s ordinarily so operated as to ell'ect, at least thereof, merely a balancing of such exothermlc reactions as may occur, and to maintain the gases and cooling of theprodu'cts The latter passfrom the soaker |2| through a line |26, wherein may be located a cooler or conin the first stages Ving coil |2| it drawn through a line |29 wherein is located a valve |30, while the uncondensed gases are with- |3| wherein is located a are fractionated before being returned to the coil |23.

As a further alternative, where hydrocarbons from the accumulator 43 are to be passed directly to the conversion system through the line 90, the overhead products from the separator |28 may be passed through a branch line |50 having a valve |5| to a suitable fractionating device indiing to the accumulator 4 While I have illustrated in the drawing a soakdiameter tubing.

'I'he polymerizedgasoline produced in accordance with the process of my invention represents will -be understood that enlarged the gases may be delivered a very advantageous and valuable product. The anti-knock value o f this gasoline is exceptionally high, for example,above 80 in octane rating. but it is predominantly non-aromatic. It will be understood by those skilled in the art that the gasoline recovered from the stabilizer 35 of Fig. i will, of course, contain a considerable proportion of cracked or reformed gasoline, and consequently may not be expected to have as high an antiknock -value as that of the'polymerlzed gasolinelike product alone. In fact, thel gasoline recovered from the stabilizer 35 of Fig. 1 represents a blended product, containing both cracked and polymerized gasoline, and consequently partakes of the characteristics of each.

While I have described my invention hereinabove with respect to various specic operating examples and details, it will readily be understood by those skilled in the art that my invention is not limited to such illustrative details or examples but may variously be vpracticed and embodied within the scope of the claims hereinafter made.

I claim:

1. A method of desulphurizing gases obtained from oil refinery operations which comprisesv separating hydrogen and methane from said gases to obtain normally gaseous hydrocarbons containing at least two carbon atoms per molecule therefrom, passing said normally gaseous hydrocarbons through a treating zone at a temperature suillciently' low and at a 'pressure sufficiently high to maintain said gases in liqueed condition, intimately contacting said gases while in liquefied state in said treating zone with an aqueous solution selected from the .group 'consisting of alkali metal carbonates .and hydroxides capable of reacting with sulphur-containing compounds in taining the sulphur compounds.

said liquefied gas, and separating the thus treated l liqueed hydrocarbons from the aqueous solution containing the sulphur compounds.

2. A method of desulphurizing gases from oil reilnery operations which comprises separating hydrogen and methane from said gases to obtain normally gaseous hydrocarbons containing at least two carbon atoms per molecule therefrom, passing said normally gaseous hydrocarbons through a treating zone at a temperature suillciently low and at a pressure sufiicientiy high to maintain said gases in liquefied condition,

intimately contacting said gases while in quelied state in said treating zone with a sodium carbonate solution capable of reacting with sulphur-containing compounds in said liquefied gas, and separating the thus treated liquefied hydrocarbons from the sodium carbonate solution con- 3. y.Il method of desulphurizing gases obtained from oil reiinery operations which comprises separating hydrogen and methane from said'gases to obtain normally gaseous hydrocarbons contain- Obtained` Y ing at least two carbon atoms per molecule therefrom, passing said normally gaseous hydrocarbons through a treating zone at a temperature suillciently low and at a pressure suillclently high to maintain said gases in liquefied condition, intimately contacting said gases whiie in liqueed state in said treating -zone with an aqueous solution of sodium hydroxide capable of reacting with sulphur-containing compounds in said liquefied gas. and separating the thus treated liquened hydrocarbons from the aqueous solution of sodium hydroxide containing the sulphur compounds.

rnaclvan c. KEITH, Jn. 

